Efficiently photocatalytic conversion of amine to imidine via perylene diimides supramolecules with oxygen vacancy

The utilization of photocatalytic oxidation technology for sustainable production of value-added chemicals has garnered significant attention. In the photocatalytic process, the transfer rate of photogenerated holes is considerably slower (2–3 orders of magnitude) than that of electrons. Consequently, the migration of photogenerated holes emerges as a critical bottleneck in achieving the efficient conversion of solar energy into value-added chemicals. To address these challenges, we synthesized a perylene diimides supramolecule with abundant oxygen vacancies (R-Ov-PDI) to enhance holes transfer processes. Photogenerated holes were selectively captured by negatively charged defect sites, triggering an attack on the C–N bond. Noticeably, the catalyst exhibited a remarkable benzylamine oxidation efficiency (31.3 mmol·g−1·h−1) under visible light, with a selectivity for imine surpassing 99%. Furthermore, it demonstrated excellent substrate generality, outperforming most reported all-organic photocatalysts by 1–2 orders of magnitude. This study prove a novel perspective for the systematic design of efficient organic photocatalysts.